CN116535094A - High-refraction optical glass and preparation method and application thereof - Google Patents
High-refraction optical glass and preparation method and application thereof Download PDFInfo
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- 239000005304 optical glass Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 25
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 7
- 230000003287 optical effect Effects 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 238000010186 staining Methods 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- 239000011521 glass Substances 0.000 description 80
- 238000004031 devitrification Methods 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000006060 molten glass Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006025 fining agent Substances 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 101000840267 Homo sapiens Immunoglobulin lambda-like polypeptide 1 Proteins 0.000 description 1
- 102100029616 Immunoglobulin lambda-like polypeptide 1 Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- -1 platinum ions Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides high-refraction optical glass, a preparation method and application thereof. The optical glass comprises the following components in percentage by weight: siO (SiO) 2 ：4～10％；B 2 O 3 ：5～15％；La 2 O 3 ：35～65％；Y 2 O 3 ：1～10％；Nb 2 O 5 ：5～15％；TiO 2 ：5～20％；WO 3 ：0～10％；ZnO：1～10％；ZrO 2 ：0.1～0.99％；Li 2 SO 4 ：0.1～1％；Al 2 O 3 ：0～10％；Sb 2 O 3 :0 to 0.1 percent; and, RO: 0-10%; wherein R is one or more than two of Ba, sr, ca, mg; the refractive index of the optical glass is 1.98-2.08, and the Abbe number is 25-32. The optical glass has low cost and excellent chemical stability, and can meet the requirements of modern novel photoelectric products.
Description
Technical Field
The invention relates to high-refraction optical glass, a preparation method and application thereof, and belongs to the field of optical glass.
Background
In recent years, the digitization and high precision of equipment using an optical system are rapidly developed, and the development trend mainly has two points on photographic equipment such as a digital camera, a video camera and the like, namely, the volume is smaller and smaller, the weight can be reduced, and the equipment is convenient for a user to carry; secondly, the imaging quality is higher and higher. The optical glass with the refractive index higher than 1.95 can greatly shorten the focal length of imaging and reduce the length required by imaging of the lens when used on optical imaging equipment, thereby greatly reducing the volume of the lens.
The appearance of the optical glass with the ultra-high refractive index makes the miniaturization and the light weight of the lens possible. Meanwhile, in the design of an optical system, miniaturization, ultra-thinning and wide angle are realized by adopting glass with a high refractive index or using an aspheric lens, and the optical system is widely used in the fields of vehicle-mounted, security protection and the like. Meanwhile, in the special optical system design, the high-refractive-index and high-Abbe-number glass can be matched with the high-refractive-index and low-Abbe-number glass to realize the purpose of compensating and correcting chromatic aberration, so that the research and development requirements of the high-refractive-index glass are gradually increased, and meanwhile, the high-refractive-index glass is applied to the long-term outdoor exposure of an optical lens for vehicle and security protection, and the requirements on water resistance and acid resistance of the optical glass are higher.
The optical glass disclosed in patent application CN100575288C, CN101570395A, CN101613184A and the like contains Gd 2 O 3 ，Gd 2 O 3 Too high a price, resulting in too high a cost. Nb in optical glass disclosed in patent application CN101497494A, CN102320738A and the like 2 O 5 Too high a content and too high a cost.
The optical glass disclosed in patent application CN 102775060A, CN105565658A and the like contains high content of BaO, the relative molecular mass of the BaO is large, and the high content of BaO can cause the excessive specific gravity of the glass.
Although the prior art discloses various optical glasses having good optical properties or low Tg temperatures, no optical glass having good optical properties, a lower Tg temperature, and low cost is disclosed.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems disclosed in the prior art, the invention firstly provides high-refraction optical glass, a preparation method thereof and an optical element. The optical glass has high refractive index, low cost, small density, excellent devitrification resistance, chemical stability and mechanical property, is suitable for being used as a digital camera and a video camera, and is easy to realize mass production.
Solution for solving the problem
The invention provides optical glass, which comprises the following components in percentage by weight:
SiO 2 ：4～10％；
B 2 O 3 ：5～15％；
La 2 O 3 ：35～65％；
Y 2 O 3 ：1～10％；
Nb 2 O 5 ：5～15％；
TiO 2 ：5～20％；
WO 3 ：0～10％；
ZnO：1～10％；
ZrO 2 ：0.1～0.99％；
Li 2 SO 4 ：0.1～1％；
Al 2 O 3 ：0～10％；
Sb 2 O 3 :0 to 0.1 percent; and
RO: 0-10%; wherein R is one or more than two of Ba, sr, ca, mg;
the refractive index of the optical glass is 1.98-2.08, and the Abbe number is 25-32.
The optical glass disclosed by the invention comprises the following components in percentage by weight:
SiO 2 ：4～8％；
B 2 O 3 ：5～12％；
La 2 O 3 ：40～60％；
Y 2 O 3 ：1～5％；
Nb 2 O 5 ：8～13％；
TiO 2 ：8～16％；
WO 3 ：0～5％；
ZnO：1～7％；
ZrO 2 ：0.1～0.95％；
Li 2 SO 4 ：0.1～0.5％；
Al 2 O 3 ：0～5％；
Sb 2 O 3 ：0～0.09％；
RO: 0-5%; wherein R is one or more than two of Ba, sr, ca, mg.
The optical glass disclosed by the invention comprises the following components in percentage by weight:
SiO 2 ：4～7％；
B 2 O 3 ：5～11％；
La 2 O 3 ：45～55％；
Y 2 O 3 ：1～3％；
Nb 2 O 5 ：8～12％；
TiO 2 ：8～14％；
WO 3 ：0～3％；
ZnO：2～6％；
ZrO 2 ：0.1～0.9％；
Li 2 SO 4 ：0.1～0.4％；
Al 2 O 3 ：0～2％；
Sb 2 O 3 ：0～0.02％；
RO:0 to 2 percent; wherein R is one or more than two of Ba, sr, ca, mg.
The optical glass according to the present invention, wherein the optical glass does not contain Ta 2 O 5 、Gd 2 O 3 And GeO 2 One or a combination of two or more of them.
The optical glass according to the present invention, wherein Nb 2 O 5 、TiO 2 、ZrO 2 And WO 3 Sum of contents Nb 2 O 5 +TiO 2 +ZrO 2 +WO 3 10-40%; and/or, tiO 2 With Nb 2 O 5 Ratio of the contents of (3) TiO 2 /Nb 2 O 5 0.3 to 2.2.
The optical glass according to the invention, wherein La 2 O 3 And Y is equal to 2 O 3 Sum of contents La 2 O 3 +Y 2 O 3 36-70%.
The optical glass according to the present invention, wherein the density ρ of the optical glass is 5.00g/cm 3 The following are set forth; the staining degree lambda of the optical glass 70 /λ 5 In lambda, lambda 70 440nm or less, lambda 5 378nm or less; the hardness HK of the optical glass is 650×10 7 Pa or more.
The optical glass according to the invention, wherein the optical glass has a water-resistant stability D W Class 1; acid resistance stability D A Class 1;
linear expansion coefficient alpha of the optical glass 20～300℃ 80X 10 -7 /K～90×10 -7 K; the transition temperature Tg of the optical glass is 680-710 ℃, and the sag temperature Ts is 730-755 ℃; the air bubble grade of the optical glass is 0-1 grade, and the foreign matter grade is 0-1 grade.
The invention also provides a preparation method of the optical glass, which comprises the steps of weighing and uniformly mixing the components according to the proportion, smelting, and then casting or leaking into a forming die or directly pressing and forming.
The invention further provides an optical element or optical preform comprising an optical glass according to the invention.
ADVANTAGEOUS EFFECTS OF INVENTION
The optical glass has a refractive index of 1.98-2.08, has low density and excellent water resistance, acid resistance stability and hardness, is low-cost and excellent chemical stability, and can meet the requirements of modern novel photoelectric products.
Detailed Description
Various exemplary embodiments, features and aspects of the invention are described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Unless otherwise indicated, all units used in this specification are units of international standard, and numerical values, ranges of values, etc. appearing in the present invention are understood to include systematic errors unavoidable in industrial production.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 10 to 40 ℃.
The optical glass of the present invention preferably does not contain expensive TeO because of the consideration of reducing the production cost 2 、Gd 2 O 3 、Ta 2 O 5 The components have refractive index of 1.98-2.08 and Abbe number of25 to 32. The composition of the optical glass of the present invention will be described in detail below, and the content of each glass component and the total content are expressed in terms of weight percent unless otherwise specified. In the following description, when a predetermined value or less or a predetermined value or more is mentioned, the predetermined value is also included.
B 2 O 3 Is a glass network forming component having the effects of reducing refractive index, improving glass meltability and devitrification resistance, reducing glass transition temperature and density, and to achieve the above effect, the present invention introduces 5% or more of B 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the However, when the amount of the polymer is more than 15%, the glass stability is lowered, surface crystallization is liable to occur, the viscosity is liable to be lowered, streaks are liable to occur, and the refractive index is lowered, and the high refractive index of the present invention cannot be obtained, and therefore, the B of the present invention 2 O 3 The content of (2) is 5 to 15%, preferably 5 to 12%, more preferably 5 to 11%.
SiO 2 Also glass forming body, and SiO 2 Formed in the glass is a three-dimensional network of silicon oxygen tetrahedra, which is very dense and firm and can strengthen B 2 O 3 The loose chain lamellar network has the functions of increasing the viscosity of molten glass, promoting stable glass formation and improving mechanical properties by mixing SiO 2 The introduction amount of (2) is controlled below 10%, so that the partial dispersion ratio of the glass can be reduced, and the rise of the glass transition temperature can be restrained; and when SiO 2 The content of (2) is too high, the liquidus temperature is increased, and the molding difficulty is increased. When SiO 2 The content of (2) is too low, and the glass crystallization property is poor. Thus, siO in the present invention 2 The content of (2) is 4 to 10%, preferably 4 to 8%, more preferably 4 to 7%.
In some embodiments, the method is carried out by mixing SiO 2 The incorporation amount of (2) is controlled to 7% or less, the specific gravity of the glass can be reduced, and the object of the present invention of high refractive index can be easily obtained, thus SiO 2 The upper limit of the content of (2) is more preferably 7%.
La 2 O 3 Is a high-refraction low-dispersion component, can raise the refractive index of glass and regulate its refractive indexDispersion, and reduced high temperature viscosity of the glass. However, when La 2 O 3 When the content of (b) is too high, the thermal stability and devitrification resistance of the glass decrease. When La is 2 O 3 When the content of (c) is too low, it is difficult to achieve desired optical characteristics. Therefore, la in the present invention 2 O 3 The content is 35 to 65%, preferably 40 to 60%, more preferably 45 to 55%.
Y 2 O 3 Has the effect of maintaining high refractive index and low dispersion, and also has the effect of improving the meltability and devitrification resistance of glass, and the Y is introduced below 10 percent 2 O 3 The reduction in thermal and chemical stability of the glass can be suppressed while maintaining a high refractive index. However, Y is 2 O 3 When the content of (2) is too high, the tendency of glass crystallization increases. However, when Y 2 O 3 When the content of (C) is too low, the glass melting property and the melting stability become poor, so that Y in the present invention 2 O 3 The content is 1 to 10%, preferably 1 to 5%, more preferably 1 to 3%.
La 2 O 3 、Y 2 O 3 The rare earth oxide is a component for improving the refractive index of the glass and improving the chemical stability of the glass, and is Gd 2 O 3 The invention has high price and does not introduce Gd 2 O 3 By introducing more than 36% of La 2 O 3 +Y 2 O 3 The above effects are obtained; however, if La 2 O 3 +Y 2 O 3 Too high, the thermal stability and devitrification resistance of the glass decrease. Therefore La 2 O 3 And Y is equal to 2 O 3 Sum of contents La 2 O 3 +Y 2 O 3 36 to 70%, preferably 40 to 65%, more preferably 40 to 60%.
WO 3 The component (A) can reduce coloring of glass caused by other high refractive index components, can increase refractive index, can lower glass transition temperature, and can improve devitrification resistance of glass. However, when the content exceeds 10%, dispersion of the glass is difficult to reach design requirements, and light transmittance of the glass in a short wavelength region of a visible light region is deteriorated. Thus, WO 3 Composition of the componentsThe content of (2) is 10% or less, preferably 5% or less, more preferably 3% or less, and even more preferably not incorporated.
Nb 2 O 5 Is a high-refraction high-dispersion component, can improve the refractive index and devitrification resistance of the glass, and reduces the thermal expansion coefficient of the glass. When the content exceeds 15%, the thermal stability of the glass tends to decrease and the liquid phase temperature tends to increase, so that Nb in the present invention 2 O 5 The content of (2) is 15% or less. When containing more than 5% of Nb 2 O 5 A lower thermal expansion coefficient can be easily obtained, and the effect of preventing glass breakage in a processing step involving temperature change such as precision press can be obtained. Thus, in the present invention, nb 2 O 5 The content of (2) is 5 to 15%, preferably 8 to 13%, more preferably 8 to 12%.
TiO 2 An optional component that can increase the refractive index and Abbe number of the glass and can improve the devitrification resistance by lowering the liquidus temperature of the glass, thus TiO 2 The lower limit of the content of the component is preferably 5%; on the other hand, by making TiO 2 The content of the component is below 20%, and the content of TiO can be reduced 2 Devitrification due to excessive content of the components can suppress the decrease in the degree of staining of the glass. Thus, tiO 2 The content of the component (A) is 5 to 20%, preferably 8 to 16%, more preferably 8 to 14%.
In some embodiments of the invention, the TiO is 2 With Nb 2 O 5 Ratio of the contents of (3) TiO 2 /Nb 2 O 5 Above 0.3, the crystallization resistance of the glass is improved, but if TiO 2 /Nb 2 O 5 Above 2.2, the glass tends to be more colored, and the light transmittance decreases. Thus, in the present invention, tiO 2 /Nb 2 O 5 May be 0.3 to 2.2, preferably TiO 2 /Nb 2 O 5 From 0.5 to 1.8, more preferably TiO 2 /Nb 2 O 5 0.9 to 1.4.
ZrO 2 The components can increase the refractive index of the glass by adding ZrO 2 The content of the components is 1% or less, whereby desired dispersion can be maintained and ZrO-induced dispersion can be suppressed 2 Is excessive of (2)The liquid phase temperature increases, crystallization performance becomes poor, and devitrification resistance is reduced. In addition, zrO 2 When the content of (2) is 0.1% or more, the refractive index and Abbe number of the glass can be increased, and the devitrification resistance can be improved. Thus, zrO 2 The content of (2) is 0.1 to 0.99%, preferably 0.1 to 0.95%, more preferably 0.1 to 0.9%.
In the present invention, nb 2 O 5 、TiO 2 、ZrO 2 、WO 3 The components have the function of improving the refractive index and the crystallization resistance of the glass, and the inventor of the invention discovers that Nb 2 O 5 、TiO 2 、ZrO 2 And WO 3 Sum of contents Nb 2 O 5 +TiO 2 +ZrO 2 +WO 3 10% or more to obtain more excellent effects. If Nb is 2 O 5 +TiO 2 +ZrO 2 +WO 3 If the light transmittance of the glass is too high, the light transmittance of the glass becomes poor, and it is difficult to obtain a low dispersion target, so that Nb 2 O 5 +TiO 2 +ZrO 2 +WO 3 10 to 40%, preferably 15 to 35%, more preferably 20 to 30%.
When the ZnO component is more than 1%, the refractive index and dispersion of the glass can be adjusted, the transition temperature is reduced, the crystallization resistance of the glass is improved, the stability of the glass is improved, and meanwhile, the ZnO can also reduce the high-temperature viscosity of the glass, so that the glass can be smelted at a lower temperature, the transmittance of the glass can be improved, and the optional components of chemical durability can be improved. On the other hand, by setting the content of the ZnO component to 10% or less, the liquid phase temperature can be reduced, and devitrification due to an unnecessary reduction in the glass transition temperature can be reduced. If the content of ZnO is more than 10%, the crucible is corroded more, and foreign matters are easily generated during melting, which affects the internal quality. Accordingly, in the present invention, the content of ZnO is 1 to 10%, preferably 1 to 7%, more preferably 2 to 6%.
Ta 2 O 5 Has the effects of improving the refractive index and the devitrification resistance of glass, but Ta 2 O 5 Is expensive, the invention does not introduce Ta 2 O 5 To reduce the material formation of glassThe cost of the optical glass can be reduced.
Li 2 SO 4 Has the functions of reducing softening temperature, improving the solubility of glass and reducing the coloring of the glass, and can be used as a clarifying agent. However, excessive introduction of the glass is not only used for reducing the refractive index of the glass and deteriorating the technological performance of the glass, but also used for increasing relative partial dispersion, and is not beneficial to forming and precise mould pressing. And Li is 2 SO 4 When the content of (B) is too high, the crystallization property is remarkably deteriorated, and the refractive index is also lowered. Thus, in the present invention, li 2 SO 4 The content of (2) may be 0.1 to 1%, preferably 0.1 to 0.5%, more preferably 0.1 to 0.4%.
RO (R is one or more of Mg, ca, sr, ba) can improve the meltability and devitrification resistance of the glass, can easily obtain a desired refractive index by controlling the content thereof to 10% or less, and can suppress devitrification of the glass caused by excessive content of these components. Therefore, the RO content of the present invention is 10% or less, preferably 5% or less, and more preferably 2% or less. In some embodiments, the inclusion of BaO may result in a deterioration in the stability of the glass, and thus it is further preferable not to introduce BaO.
CaO helps to increase the refractive index of the glass, which can increase the glass forming range by replacing part of BaO. However, if CaO is added excessively, the crystallization resistance of the glass is lowered. Therefore, the CaO content is limited to 0 to 5%, preferably 0 to 2%
The addition of SrO to glass can adjust the refractive index and Abbe number of the glass, but if the addition amount is too large, the glass stability and crystallization resistance can be reduced, and the cost of the glass can be increased rapidly. Therefore, the SrO content is limited to 0 to 5%, preferably 0 to 2%.
Although MgO contributes to the improvement of the chemical stability of glass, if the content of MgO is too large, the refractive index of the glass cannot meet the design requirement, the crystallization resistance and the chemical stability of the glass are reduced, and meanwhile, the cost of the glass is rapidly increased. Therefore, the MgO content is limited to 0 to 5%, preferably 0 to 2%.
Introducing Al in small amounts 2 O 3 Can improve the stability and chemical stability of glass formation, but the content thereof exceedsWhen the content exceeds 10%, the glass-melting property tends to be deteriorated and the devitrification resistance tends to be lowered, so that Al of the present invention 2 O 3 The content of (2) is 10% or less, preferably 5% or less, more preferably 2% or less, and even more preferably not incorporated.
By incorporating 0-0.1% of Sb 2 O 3 As the fining agent, 0 to 0.09% of the fining agent is preferably introduced, more preferably 0 to 0.02% of the fining agent is introduced, and even more preferably no Sb is introduced, so that the fining effect of the glass can be improved 2 O 3 。
In the optical glass of the present invention, the oxide of a transition metal such as V, cr, mn, fe, co, ni, cu, ag and Mo is colored even when contained in a small amount alone or in combination, and absorbs at a specific wavelength in the visible light range, thereby reducing the visible light transmittance of the present invention, and therefore, in particular, the optical glass which is required to have a transmittance at a wavelength in the visible light range is preferably practically not contained.
Th, cd, tl, os, be and Se oxides have a tendency to be used in a controlled manner as harmful chemical substances in recent years, and are required to provide environmental protection not only in the glass manufacturing process but also in the processing steps and disposal after production. Therefore, in the case where the influence on the environment is emphasized, it is preferable that they are not substantially contained except for unavoidable mixing. As a result, the optical glass becomes practically free from environmental pollutants. Therefore, the optical glass of the present invention can be manufactured, processed, and discarded without taking special measures against the environment.
In order to achieve environmental friendliness, the optical glass of the present invention does not contain As 2 O 3 And PbO. Although As 2 O 3 Has the effects of eliminating bubbles and better preventing glass from being colored, but As 2 O 3 The addition of (c) increases the corrosion of the glass to the furnace, and in particular to the platinum of the platinum furnace, resulting in more platinum ions entering the glass, which adversely affects the service life of the platinum furnace. PbO can significantly improve the high refractive index and high dispersion properties of glass, but PbO and As 2 O 3 Substances causing environmental pollution。
The term "not incorporated" as used herein means that the compound, molecule, element or the like is not intentionally added as a raw material to the optical glass of the present invention; however, it is also within the scope of the present invention that certain impurities or components may be present as raw materials and/or equipment for producing optical glass that are not intentionally added, and that may be present in small or trace amounts in the final optical glass.
In the present invention, the optical glass has a density ρ of 5.00g/cm 3 The following are set forth; the degree of staining lambda 70 /λ 5 In lambda, lambda 70 440nm or less, lambda 5 378nm or less; hardness HK of 650×10 7 Pa or more. Water resistance stability D of the optical glass W Class 1; acid resistance stability D A Class 1; linear expansion coefficient alpha of the optical glass 20～300℃ 80X 10 -7 /K～90×10 -7 K; the transition temperature Tg of the optical glass is 680-710 ℃, and the sag temperature Ts is 730-755 ℃; the air bubble grade of the optical glass is 0-1 grade, and the foreign matter grade is 0-1 grade.
The present invention also provides an optical preform and an optical element formed from the above optical glass according to methods well known to those skilled in the art. The optical glass has high refractive index, so the optical element also has high refractive index, and can be applied to equipment such as digital cameras, digital video cameras, camera phones and the like.
The invention further provides a preparation method of the optical glass, which comprises the steps of weighing and uniformly mixing the components according to the proportion, smelting, and then casting or leaking into a forming die or directly pressing and forming.
Specifically, raw materials (such as oxides, hydroxides, carbonates, nitrates and the like) of each component of the optical glass are placed in a smelting furnace (such as a platinum crucible, an alumina crucible and the like) at 1350-1460 ℃, and after melting, clarifying, stirring and homogenizing, homogeneous molten glass free of bubbles and undissolved substances is obtained, and the molten glass is cast and annealed in a mold or directly pressed and formed.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In order to further understand the technical scheme of the present invention, embodiments of the optical glass of the present invention will now be described. It should be noted that these examples do not limit the scope of the present invention.
The optical glasses (examples 1 to 20) shown in tables 1 to 3 were obtained by weighing and mixing common raw materials for optical glasses (such as raw materials of lanthanum oxide, yttrium oxide, silicon oxide, calcium carbonate, calcium nitrate, aluminum hydroxide, boric acid, etc.) in accordance with the ratios of the respective examples shown in tables 1 to 3, placing the mixed raw materials in a platinum crucible of a melting apparatus, melting, clarifying, stirring and homogenizing at a temperature of 1350 to 1460 ℃ to obtain a homogeneous molten glass free of bubbles and undissolved substances, and casting and annealing the molten glass in a mold.
Performance testing
1. Refractive index n d Abbe number v d
The refractive index n of the obtained optical glass is carried out according to the test method of GB/T7962.1-2010 d Abbe number v d N listed in the table d 、υ d Is the data after annealing at-4 ℃.
2. Knoop hardness HK
Knoop hardness was measured according to the test method specified in ISO 9385.
3. Average linear expansion coefficient alpha of glass 20/300℃
The measurement was carried out according to the method specified in GB/T7962.16.
4. Transition temperature Tg and sagging temperature Ts
The measurement was carried out according to the method specified in GB/T7962.16.
5. Density ρ
The density of the obtained optical glass was measured according to the test method of GB/T7962.20-2010.
6. The degree of staining lambda 70 /λ 5
Coloring degree lambda for optical glass shortwave transmission spectrum characteristic 70 /λ 5 And (3) representing. Wherein lambda is 70 Refers to the corresponding wavelength lambda when the transmittance of the glass reaches 70 percent 5 Refers to the wavelength corresponding to the glass transmittance reaching 5%.
7. Water resistance D W Acid resistance D A
Water resistance D of chemical stability of the obtained optical glass according to a test method of JB/T10576-2006 W Acid resistance D A Testing was performed.
8. Bubble degree and foreign matter grade
According to GB/T7962.8-2010 colorless optical glass test method part 8: bubble degree the obtained optical glass was tested for bubble degree and foreign matter grade.
Refractive index n of the optical glasses prepared in examples 1 to 20 d Abbe number v d Hardness HK, expansion coefficient, transition temperature Tg, sagging temperature Ts, density ρ, lambda in staining degree 70 And lambda (lambda) 5 Water resistance D W Acid resistance D A The same is shown in tables 1-3.
Table 1: glass Components and Performance parameters of examples 1-7
Table 2: glass Components and Performance parameters of examples 8-14
Table 3: glass Components and Performance parameters of examples 15-20
As can be seen from the above examples, the refractive index (n d ) Is 1.98 to 2.08, abbe number (. Nu) d ) 25 to 32, and the density rho is 5.00g/cm 3 The following are set forth; the hardness HK of the optical glass was 650X 10 7 Water resistance stability D of Pa or above W Class 1, acid resistance stability D A Class 1; the coloring degree lambda 70/lambda 5 of the optical glass is lambda 70 440nm or less, lambda 5 Is 378nm or less. In addition, the linear expansion coefficient alpha of the optical glass 20/300℃ 80X 10 -7 /K～90×10 -7 K; the transition temperature Tg of the optical glass is 680-710 ℃, and the sag temperature Ts is 730-755 ℃; the optical glass has a bubble level of 0-1 and a foreign matter level of 0-1, and is suitable for wide application in digital cameras, digital video cameras, camera phones and other devices.
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. The optical glass is characterized by comprising the following components in percentage by weight:
SiO 2 ：4～10％；
B 2 O 3 ：5～15％；
La 2 O 3 ：35～65％；
Y 2 O 3 ：1～10％；
Nb 2 O 5 ：5～15％；
TiO 2 ：5～20％；
WO 3 ：0～10％；
ZnO：1～10％；
ZrO 2 ：0.1～0.99％；
Li 2 SO 4 ：0.1～1％；
Al 2 O 3 ：0～10％；
Sb 2 O 3 :0 to 0.1 percent; and
RO: 0-10%; wherein R is one or more than two of Ba, sr, ca, mg;
the refractive index of the optical glass is 1.98-2.08, and the Abbe number is 25-32.
2. The optical glass according to claim 1, wherein the optical glass comprises the following components in weight percent:
SiO 2 ：4～8％；
B 2 O 3 ：5～12％；
La 2 O 3 ：40～60％；
Y 2 O 3 ：1～5％；
Nb 2 O 5 ：8～13％；
TiO 2 ：8～16％；
WO 3 ：0～5％；
ZnO：1～7％；
ZrO 2 ：0.1～0.95％；
Li 2 SO 4 ：0.1～0.5％；
Al 2 O 3 ：0～5％；
Sb 2 O 3 ：0～0.09％；
RO: 0-5%; wherein R is one or more than two of Ba, sr, ca, mg.
3. The optical glass according to claim 2, characterized in that it comprises, in weight percent:
SiO 2 ：4～7％；
B 2 O 3 ：5～11％；
La 2 O 3 ：45～55％；
Y 2 O 3 ：1～3％；
Nb 2 O 5 ：8～12％；
TiO 2 ：8～14％；
WO 3 ：0～3％；
ZnO：2～6％；
ZrO 2 ：0.1～0.9％；
Li 2 SO 4 ：0.1～0.4％；
Al 2 O 3 ：0～2％；
Sb 2 O 3 ：0～0.02％；
RO:0 to 2 percent; wherein R is one or more than two of Ba, sr, ca, mg.
4. An optical glass according to any one of claims 1 to 3, wherein the optical glass does not contain Ta 2 O 5 、Gd 2 O 3 And GeO 2 One or a combination of two or more of them.
5. The optical glass according to any one of claims 1 to 4, wherein Nb 2 O 5 、TiO 2 、ZrO 2 And WO 3 Sum of contents Nb 2 O 5 +TiO 2 +ZrO 2 +WO 3 10-40%; and/or, tiO 2 With Nb 2 O 5 Ratio of the contents of (3) TiO 2 /Nb 2 O 5 0.3 to 2.2.
6. According to any one of claims 1 to 5The optical glass is characterized in that La 2 O 3 And Y is equal to 2 O 3 Sum of contents La 2 O 3 +Y 2 O 3 36-70%.
7. The optical glass according to any one of claims 1 to 6, wherein the optical glass has a density ρ of 5.00g/cm 3 The following are set forth; the staining degree lambda of the optical glass 70 /λ 5 In lambda, lambda 70 440nm or less, lambda 5 378nm or less; the hardness HK of the optical glass is 650×10 7 Pa or more.
8. The optical glass according to any one of claims 1 to 7, wherein the optical glass has a water-resistant stability D W Class 1; acid resistance stability D A Class 1;
linear expansion coefficient alpha of the optical glass 20～300℃ 80X 10 -7 /K～90×10 -7 K; the transition temperature Tg of the optical glass is 680-710 ℃, and the sag temperature Ts is 730-755 ℃; the air bubble grade of the optical glass is 0-1 grade, and the foreign matter grade is 0-1 grade.
9. A method for producing an optical glass according to any one of claims 1 to 8, comprising weighing the components in proportion, mixing them uniformly, melting them, and casting or leaking into a molding die or directly press-molding.
10. An optical element or optical preform comprising an optical glass according to any one of claims 1 to 8.
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